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Title: Modular Design of Multifunctionality in TCNQ-Based Fe(II) Spin Crossover Complexes
Fe(II) coordination complexes with ligands of an intermediate field strength often show witching between the high-spin (HS) and low-spin (LS) electronic configurations, known as spin crossover (SCO). This spin-state conversion is achieved by changes in temperature, pressure, or photoexcitation, which make SCO complexes promising materials for various applications that rely on bistable systems. Multifunctional materials that exhibit both spin-state switching and conductivity can be created by combining Fe(II) SCO complexes with organic TCNQ-type electron acceptors. In such complexes, TCNQ●d– radical anions are typically arranged in layers of one-dimensional stacks that provide conducting pathways (Fig. 1). The stacking distance can be affected by structural changes induced by the alteration in the electronic configuration and, thus, bond lengths at the Fe(II) center, resulting in synergy between SCO and conductivity. The synthesis of such materials can be approached in two ways: (1) by coordinating TCNQ●d– ligands directly to the Fe(II) center, which is partially protected by blocking ligands that limit the growth of extended structures or (2) by co-crystallizing completely blocked Fe(II) centers with free TCNQ●d– radicals. We will discuss several examples of the second approach, in which homoleptic Fe(II) cationic SCO complexes with tridentate 2,6-bispyrazolyl-pyridine (bpp) type ligands have been co-crystallized with fractionally-charged TCNQ●d– radical anions. The temperature- and solvent-dependent magnetic behavior and transport properties of these materials will be discussed. We will also present new pathways to improve the design of such molecule-based conductors with spin-state switching properties. To the best of out knowledge, we report the first examples of Fe(II) based conducting molecular materials with abrupt temperature-driven spin transitions.  more » « less
Award ID(s):
1955754
NSF-PAR ID:
10225718
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
National Meeting of the Anerican Chemical Society
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  2. null (Ed.)
    Spin crossover (SCO) is a phenomenon observed for certain transition metal complexes with electronic configuration 3d4-3d7. The conversion between the low-spin (LS) and high-spin (HS) states is usually driven by a variety of external perturbations, such as temperature, pressure, or light. The switching between the enthalpically preferred LS state and entropically favorable HS state is accompanied by dramatic changes in the metal-ligand bond lengths, unit cell volume, optical absorption spectrum, and magnetic susceptibility.1 These changes make SCO materials suitable for applications in sensors, memory, and display devices. One of the central challenges in the SCO research is to initiate strongly cooperative interactions known to lead to abrupt spin transitions and thermal hysteresis that can be harvested as a memory effect. One of the strategies to enhance the cooperativity is to design SCO complexes with supramolecular interactions such as π-stacking of aromatic fragments or hydrogen bonding.2 In this work, we report syntheses and characterization of heteroleptic complexes of [Fe(tpma)(L)](ClO4)2 (tpma = tris(pyridin-2-ylmethyl)amine) with novel π-extended biimidazole-type ligands (L) bearing 2,3-dimethyl-naphthalene-, 6,7-dimethyl-2,3-diphenyl-quinoxaline, and 2,3-dimethyl-anthracene pendant fragments. Solvent-free naphthalene-functionalized complex [Fe(tpma)(xnap-bim)](ClO4)2 exhibits abrupt spin transition at T1/2 = 127K with a narrow 1 K hysteresis loop. In contrast, polymorph of this complex that contains one interstitial molecules of pyridine exhibits gradual SCO. Anthracene-functionalized complex [Fe(tpma)(anthra-bim)](ClO4)2 also crystallizes as two polymorphs. Structural studies at 100, 230, and 300 K revealed dramatic changes in the N-Fe-N biting angles and Fe-N distances, indicating the occurrence of temperature-induced SCO. Complex [Fe(tpma)(quin-bim)](ClO4)2 (quin-bim = 6,7-dimethyl-2,3-diphenyl-quinoxaline-2,2’-biimidazole) showed only HS state at 100 and 230 K. In the crystal packing the mononuclear cations form stacks along b axis. We discuss how the observed magnetic behavior correlates with changes in the crystal packing and interactions between the pendant aromatic substituents on the aforementioned complexes. 
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  3. Abstract

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